Aromatic and aromatic/heteroaromatic molecular structures with controllable electron conducting properties

ABSTRACT

Aromatic and aromatic/heteroaromatic molecular structures with controllable electron conducting properties are derived from the incorporation of electron active substituents in selective positions.

This application claims the benefit of U.S. Provisional Application60/429,169, filed Nov. 26, 2002.

FIELD OF INVENTION

The invention is directed to the preparation of novel aromatic andaromatic/heteroaromatic molecular structures with controllable electronconducting properties which can form self-assembled layers on metal orother substrates, and can be used in molecular scaled electronicdevices.

BACKGROUND

The expanding commercial interest in the generation of small nano-scaleelectronic devices highlights a need for the generation of a new classof conductive molecules that are functionalized for use innano-electronic device fabrication. However, the discovery of newconductive molecules for this is fraught with difficulty. For example,little is known about the specifics of how conductive molecules work.Additionally, it is difficult to connect conductive molecules toelectrodes and even more difficult to perform conductivity measurementson single molecules. In addition to the difficulties in construction,the design of new molecules possessing useful properties is hampered bythe lack of a facile method for correlating the effects of opticaltransitions to electronic molecular properties. Once a structure isdesigned, the synthesis, purification and growth of single crystals ofmolecules as large as these is not easily accomplished. Typically,multistep separations are required. Finally, the coupling of differentaromatic and heteroaromatic building blocks is difficult to achievebecause substituted structures are prone to side reactions and longreaction times.

In spite of these difficulties a number of conductive molecules havebeen synthesized. For example, Tours et al (WO 00/01360; (S. J. Tour,Acc. Chem Res., 33, 791, 2000) teaches the assembly of molecularstructures consisting of phenylene/ethynylene units and the measurementof the resistance/conductivity of a self-assembled monolayer depositedon a pattern of electrodes. Very few of these structures have beendemonstrated to display distinct negative differential resistance (NDR)(increased resistance with increasing driving voltage) and then onlyunder specific conditions, mostly at low temperatures.

Additionally several groups (J. Chen, et al, Science, Vol 286, pg. 1550,1999; E. W. Wong et al, JACS, 2000, 122, 5821-5840; have synthesizedconducting molecules and measured the negative differential resistancebehavior and conductivity of a monolayer of this material between twosurfaces. C. P. Collier et al, (Science, vol. 285, 16 Jul. 1999) havesynthesized rotaxanes and catenanes molecules, made monolayers of thesemolecules using Langmuir-Blogett techniques, and demonstrated resonanttunneling current flow derived from the reversible inter-conversionbetween two different states.

The above listed references teach the synthesis of useful compounds,however do not address the need for functionalized moleculesspecifically adapted for facile nano-device fabrication.

Applicants have met the stated need with the design and synthesis ofnovel aromatic and aromatic/heteroaromatic having specific substituentsuseful for the incorporating these molecules into nano-electronicdevices.

SUMMARY OF THE INVENTION

The invention provides new aromatic/heteroaromatic conducting moleculesuseful in nano-electronic devices and methods of making the same. Themolecules of the invention may additionally comprise barrier groups(—CH₂, cyclic, etc.) and are versatile, allowing for the assembly ofmolecular components (possessing different terminal groups) in two orthree dimensions.

Accordingly the invention provides a conducting molecule according toFormula I, II, or III:

-   wherein R is independently selected from the group consisting of:

-   wherein A is independently selected from the group consisting of H,    a C1-C6 alkyl group, F, —CN, and —S—C(═O)—CH₃, wherein at least one    of F, —CN, and —S—C(═O)—CH₃ is present;-   and B is selected from the group consisting of:

-   wherein B is optionally substituted with H, a C1-C6 alkyl group, F,    —CN, —NO₂, and —S—C(═O)—CH₃.

Additionally the invention provides a molecular based memory system,molecular wire, or molecular switch, comprising the composition of theinvention.

In another embodiment the invention provides a process for synthesizinga supramolecular structure comprising the steps of:

-   -   (a) providing a conducting molecule of the invention;    -   (b) providing a suitable substrate;    -   (c) contacting the conducting molecule of (a) with the substrate        of (b) wherein the conducting molecule is immobilized on the        substrate;    -   (d) contacting the immobilized conducting molecule of (c) with a        redox or photochemical reagent under conditions wherein the        immobilized conducting molecule is activated; and    -   (e) contacting the activated conducting molecule with the        conducting molecule of step (a) wherein molecular addition takes        place and a supramolecular structure is formed.

In an alternate embodiment the invention provides a supramolecularstructure synthesized by a process of the invention as well as sensorscomprising the same.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the x-ray crystal structure of1,4-bis(4-pyridyl)butadiyne), example 1.

FIG. 2 shows the x-ray crystal structure of4-ethynyl(pyridine)-4′-ethynylphenyl-5′-nitro-1 pyridine, example 2.

FIG. 3 shows the x-ray crystal structure of 4-ethynyl(1,2-dicyanobenzene) 4′-ethynylphenyl-1(4,5-dicyanobenzene), example 5.

FIG. 4 shows the x-ray crystal structure of1-thioacetyl-4(4′-fluoro-1′-(ethynyl)phenyl)benzene, example 9.

FIG. 5 shows the x-ray crystal structure of4-ethynyl(2-fluoro-cyanobenzene)-4′-ethynylphenyl-1(2-fluoro-cyanobenzene), example 10.

FIG. 6 is a graph of the index of refraction (n) and the extinctioncoefficient (k) versus wavelength lambda (λ) for the self assembledmolecules of example 9, PETB.

FIG. 7 is a graph of the index of refraction (n) and the extinctioncoefficient (k) versus wavelength lambda (λ) for the self assembledmolecules of example 10, pF-PETB.

FIG. 8 is a graph of the index of refraction (n) and the extinctioncoefficient (k) versus wavelength lambda (λ) for the self assembledmolecules of example 11, 3N-PETB.

FIG. 9 is a graph of the index of refraction (n) and the extinctioncoefficient (k) versus wavelength lambda (λ) for the self assembledmolecules of example 12, 3-PETB.

FIG. 10 is a graph of the index of refraction (n) and the extinctioncoefficient (k) versus wavelength lambda (λ) the self assembledmolecules of example 13, 2F2CN3B.

FIG. 11 is a graph comparing the index of refraction (n) and theextinction coefficient (k) versus wavelength lambda (λ) for the selfassembled molecules of examples 9, PETB, 10, Pf-petb, 11, 3N-PETB, 12,3-PRTB and 13, 2F2CN3B.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the design, synthesis, self-assembly andprocessing in the solid state of organic molecules with controllableelectron conducting, semiconducting, insulating properties and/or switchcharacteristics derived from the presence of appropriate electron activesubstituents placed in selective positions of the aromatic andheteroaromatic structures.

The present compounds advance the art in that they are robust enough toallow for molecular manipulation at different temperatures andconditions. The present compounds may be used in the synthesis ofthree-terminal devices, logic switches and other nano-electronicdevices.

Additionally the compounds of the invention can function as activeelements in electronic devices such as in SAMs for random-access-memorydevices where data can be written, read and erased, or in sensors.Similarly, single molecules can be used as molecular wires and/ormolecular switches. Wires and switches are the most basic components ofmemory and logic devices and components comprised of the presentmaterials will play a critical role in reducing the size of today'scomputer circuits.

The following definitions and abbreviations may be used for theinterpretation of the claims and the specification.

“SAM” is the abbreviation for “self assembled monolayer”.

“SA” is the abbreviation for “self assembly”.

As used herein, “alkyl” means an alkyl group containing up to 6 carbonatoms. Common examples of such alkyl groups include methyl, ethyl,propyl, isopropyl, butyl, s-butyl, isobutyl, pentyl, neopentyl, hexyl,and cyclohexyl. The alkyl group may be linear, branched, or cyclic.

Within the context of the molecular formulae illustrated herein, theattachment points of the groups designated as “R” and B” are indicatedby

, and unless specifically attached to a position on the ring the pointof attachment can be at any open position of the designated ring.

The term “conducting molecule” means any molecule that has the abilityto conduct a flow of electrons from one end of the molecule to theother.

The term “supramolecular structure” means a complex of at least two, andpreferably a plurality of conducting molecules. Supramolecularstructures of the invention may be formed through the self-assembly ofconducting molecules.

As used herein the term “molecular based memory system” refers to amolecule or set of molecules that have the ability to alter itsconductivity by storing electrons.

The term “molecular wire” means any molecular structure that allows theflow of electrons from one end to the other end of the structure. In apreferred embodiment molecular wires of the invention will comprise atleast two terminals for contacting additional components of anano-electronic device.

The term “molecular switch” is used interchangeably with “controllablewire” and refers to a molecular structure where the electron flow can beturned on and off on demand. In a preferred embodiment a molecularswitch will both switch and amplify the current. In some embodimentsmolecular switches can have a number of different terminals, where thetwo terminal and three terminal conformations are typical. In the threeterminal case, one terminal functions as the source of the current whilethe second terminal functions as the drain. The third terminal in theswitch functions as the gate and acts to vary the electricalconductivity of the device. Assemblies of molecular wires and switchescan be interconnected to produce complex circuitry for use as logic ormemory or interconnection devices. (see for example M. Reed and J. Tour,Scientific American, June 2000, pages 86-93 and Molecular Electronics:Science and Technology, Edited by A. Aviram and M. Ratner. Annals of theNew York Academy of Sciences, vol. 852; 1998.)

The invention provides conducting molecules having substituentsstrategically placed within the molecule which affect the electricalconducting properties of the molecule.

Design and Synthesis of Conducting Molecules

It is one object of the present invention to design and prepareconducting molecules in such a manner so as to control the electronicconduction properties of the resulting compounds. A number of possiblebuilding blocks for preparation are possible, where aromatic andaromatic/heteroaromatic molecules are preferred. These may be linkedtogether in configurations in which π low energy orbitals aredelocalized from one end to the other end of the molecule byincorporating specific types of electron-active groups as substituentsin selected positions.

The aromatic and or aromatic/heteroaromatic structures of the presentinvention are synthesized via cross-coupling reactions of halogenatedaromatic compounds with terminal aromatic acetylenes as illustrated inthe examples. Various electron active, withdrawing (F, CF₃, SO₂CF₃) anddonating ((N(CH₃)₂, N(C₂H₅)₂) groups are used to substitute differentpositions of the aromatic and heteroaromatic rings in order to vary theconduction properties and/or achieve controlled response with voltagefluctuations. The ends of these molecules are individuallyfunctionalized with groups such as SH, pyridine, CN, SCN, etc. topromote the absorption and self-assembly (SA) on metal surfacesincluding Au, Cu, Pd, Pt, Ni, Al, Al₂O₃, etc. The ability of thesegroups to promote molecular self-assembly has been well documented (seefor example George M. Whitesides; Scientific American, September 1995).The SA may be achieved either by microcontact printing or flooding themetal surfaces or both.

In some instances it will be useful to further functionalize themolecules of the invention to enhance their ability to bind to varioussubstrates. For example functional end groups such as SCN, NH₂ can beutilized as binding sites for biological and other molecules. Biologicalmaterials that can be bond in this manner include but are not limited tonucleic acid (DNA, RNA and peptide nucleic acids (PNA)), proteins,lipids and complex macromolecules comprising combinations of the same.End groups of this sort are referred to herein as “alligator clips” or“molecular fragments” for their ability to link up with other molecules.The use of alligator clip functionalization will permit the constructionof hybrid organic/inorganic/biological devices. For example it isexpected that molecules having these functional groups could interactwith DNA by intercalating one or more aromatic groups between base pairsof the double helix. Such molecules are expected to have applications inbiosensors or other biomedical devices as described for example by Lokeyet al., Journal of the American Society, 119, pp. 7202-7210, 1997 Inother applications binding to various metals will be useful. In theseapplications the use of co-absorption of two types of molecules, oneelectron-donor and the other electron acceptor to the metal, is expectedto lead to the formation of ordered SA surface structures with bothmolecules in the same surface unit cell. The molecules of the inventioncombine the ability to electron conduct/insulate and/or switch with theability to build self-assembled mono- or multilayers and supramolecularobjects that are neither mono nor layers and are thus particularlyuseful in the construction of nano-electronic devices.

Several aids are available in the design of the molecules of theinvention. For example changes in optical absorption characteristicsderived from structural variations of molecular self-assembliesmonitored by spectroscopic ellipsometry (SE) can be correlated withinterband transitions and used to directly demonstrate the control ofelectronic properties. These techniques may be used to determine theeffectiveness of various substituents to alter electrical conductingproperties in the molecules of the invention.

Synthesis of Conducting Supramolecules

Once the conducting molecule is designed it may be assembled intomolecular conglomerates or supramolecules having conducting properties.Redox chemistry and photochemistry make use of the alligator clipfunctionality and can be used to build up supramolecular objectssequentially.

For example a first molecule (M1) comprising a plurality of functional“alligator clip” groups may be redox reacted (by gas exposure orphotoexcitation) resulting in the disassociation of the clips. A secondor third molecule (M2 or M3) may then be contacted with the reacted M1where self-assembly will take place. Additional units may be added tothe complex in a similar fashion by repeating the process. Thesequential nature of this molecular construction is particularlyeffective in the construction of supermolecular switches and sensingdevices.

Once assembled it may be useful to immobilize these supramolecularstructures on a solid support in a patterned or unpatterned fashion ascomponents in nano-electronic devices. It is contemplated that at leasttwo and preferably a plurality of these supramolecular structures may belaid down on a substrate. Suitable substrates for this purpose include,but are not limited to silicon wafers, synthetic polymer supports, suchas polystyrene, polypropylene, polyglycidylmethacrylate, substitutedpolystyrene (e.g., aminated or carboxylated polystyrene;polyacrylamides; polyamides; polyvinylchlorides, etc.), glass, agarose,nitrocellulose, nylon, nickel grids or disks, carbon supports,aminosilane-treated silica, polylysine coated glass, mica, andsemiconductors such as Si, Ge, and GaAs.

When a conducting molecule is fixed to the surface of a substrate it maybe contacted with a redox of photochemical reagent which results in theactivation of the molecule. By “activation” it is meant that aconducting molecule is treated in a manner whereby it is disposed toreacting with other conducting molecules for the generation of asupramolecular structure. The activated molecules are then contactedwith additional conducting molecules and supramolecular structures aresequentially constructed.

The conductive molecules of the invention are expected to have metallic(ohmic) and in some cases semiconductive behavior. These behaviors lendthemselves to the use of these compounds both as interconnects and asactual electronic devices (e.g., switches, logic gates). In oneinstance, the conductive molecules are expected to be able to linknanometer scale electronic devices together permitting the fabricationof high-density electronic circuits. It is contemplated that it will bepossible to array these compounds in a crossed arrangement, where thedistance between adjacent molecules can be controlled by the potentialdifference between them, then the array could be used as a non-volatilememory device. Examples of such construction is described by Rueckes T.et al. (2000). Science 289, 94-97 for carbon nanotubes. Semiconductingmolecules could find use in 3-terminal gated devices which can be useddirectly as switches, amplifiers or logic gates. Other possibleapplications include point sources for emission in field-emissiondisplay devices and as conductive inclusions in conductive coatings.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

General Methods

Unless otherwise specified below all chemical reagents were obtainedfrom the Sigma Chemical Co. (St. Louis, Mo.) or Aldrich (Milwaukee,Wis.).

The meaning of abbreviations is as follows: “h” means hour(s), “min”means minute(s), “sec” means second(s), “d” means day(s), “mL” meansmilliliters, “L” means liters.

Example 1 Preparation of 1,4-Bis(4-Pyridyl)Butadiyne) Reagents UsedInclude:

-   -   4-Ethynylpyridine hydrochloride: 97%, Mw=139.58, Mp 150° C.,    -   Aldrich: 53, 092-1    -   Diethyl Ether: Mw=74.12 d=0.713, Bp 35-36° C.    -   Triethylamine: Mw=101.19 d=0.726, Mp −115° C., Bp 88.8° C.,    -   Aldrich: 47,128-3    -   Copper (I) Chloride: Mw-98.99, Mp 430° C., Aldrich: 22, 962-8    -   Oxygen: Mw=32, Mp-218° C., Bp-183° C., Aldrich: 29,560-4    -   4-Ethynylpyridine: Mw=103.1237, Mp 95-96° C.,    -   Pyridine: Mw=79.10, D=0.983, Bp 115-115° C. Aldrich: 27,097-0

This compound was synthesized by oxidative coupling of 4-ethynylpyridine (freshly prepared from its hydrochloride form as describedbelow) in pyridine in the presence of copper (I) chloride according tothe following reaction scheme:

Crystallization from carbon tetrachloride gave colorless plates with thefollowing structure as determined from X-ray diffraction data.

Crystal Data: C₁₄H₈N₂, from carbon tetrachloride, colorless, irregularplate, ˜0.450×0.330×0.020 mm, monoclinic, P21/n, a=3.759(6) Å,b=22.95(3) Å, c=5.801(8) Å, beta=90.02(3)°, Vol=500.4(13). The crystalstructure is shown in FIG. 1.

A modified procedure for the Sonagashira coupling methodology was usedas described in J. A. Whiteford et al., J. Am. Chem. Soc., 119,2524-2533, (1997) and L. D. Ciana et al., J. Heterocycl. Chem. 1984,607-608. Free 4-ethynylpyridine was obtained by reacting 4.19 g (30.0mmol) of 4-ethynylpyridine hydrochloride with 4.18 mL (30.0 mmol) oftriethylamine in 50 mL of diethyl ether at room temperature over night.2.6 g (25.2 mmol) 4-ethynylpyridine, 50 mL (621 mmol) pyridine, and 0.2g (2.02 mmol) copper (I) chloride were charged into a 250 mL Schlenkflask with a stir bar. Oxygen was then bubbled into the solution via alecture bottle of O₂ connected to a ⅛ inch Teflon® tubing. The reactionwas stirred for 45 minutes at room temperature and pressure. Theprecipitate appeared after 10 minutes. The precipitate was then filteredand washed with water and dried in a dry box in the absence of light.The resulting compounds were subjected to several crystallization stepsuntil pure crystals were obtained. The crude product can also bepurified by sublimation (15 torr and 70° C.) or by recrystallizationusing carbon tetrachloride, which yields colorless plates of theproduct.

Other compounds were synthesized or can be synthesized by Sonogashirareaction using palladium (0)/CuI catalyzed cross coupling of aromatichalides with terminal acetylenes according to the following generalreaction scheme:

The coupling reactions were carried out in a heavy-walled flask. Acatalytic system such as: bis-(dibenzylideneacetone palladium)(0),Pd(dba)₂) (2 mol %), triphenylphosphine (Pd catalyst/ligand=1:1), copper(I) iodide and triethylamine and the aromatic halide, carefully handledin a dry box and introduced in the flask. The flask was evacuated andback-filled with nitrogen several times prior the addition of thearomatic terminal acetylene. All these procedures were carried out in adry box. The flask was then sealed and moved to a regular hood andheated if necessary to 70° C. for 24 hours with stirring. The solventwas evaporated under vacuum and the residue was purified by flashchromatography. The resulting product was recrystallized fromappropriate solvents. When necessary the products were subjected toseveral crystallization steps until pure crystals were obtained.

Example 2 Preparation of4-Ethynyl(Pyridine)-4′-Ethynylphenyl-5′-Nitro-1-Pyridine

This compound was synthesized as described above in Example 1.Crystallization from ethanol gave colorless needles with the followingstructure as determined from X-ray diffraction data. The crystalstructure is shown in FIG. 2. It can be seen that the mean plane of theouter rings forms an angle of 28.3 degrees with the inner ring.

Crystal Data: C₂₀H₁₁N₃O₂, from ethanol, colorless, needle,0.220×0.020×0.020 mm, monoclinic, C2/c, a=16.351(3) Å, b=11.659(3) Å,c=9.2685(19) Å, beta=117.706(5)°, Vol.=1564.3(6) Å3, Z=4, T=−100° C.,Formula weight=325.32, Density=1.381 mg/m3, μ(Mo)=0.09 mm⁻¹.

Example 3 Preparation of4-Ethynyl(Pyridine)-4′-EthynylBiphenylene-1-Pyridine

4-Ethynyl(pyridine)-4′-ethynylbiphenylene-1-pyridine can be synthesizedaccording to the procedure outlined in Example 1 via the reaction schemeshown above.

Example 4 Preparation of4-Ethynyl(Pyridine)-4′-EthynylNaphthalene-1-Pyridine

4-Ethynyl (1,2-dicyanobenzene) 4′-ethynylphenyl-1(4,5-dicyanobenzene)can be synthesized according to the procedure outlined in Example 1 viathe reaction scheme shown above.

Example 5 Preparation of 4-Ethynyl(1,2-dicyanobenzene)-4′-Ethynylphenyl-1(4,5-dicyanobenzene)

4-Ethynyl (1,2-dicyanobenzene)-4′-ethynylphenyl-1(4,5-dicyanobenzene)was synthesized according to the procedure outlined in Example 1 via thereaction scheme shown above.

Crystallization from methylene chloride gave colorless needles with thefollowing structure as determined from X-ray diffraction data. Thecrystal structure is shown in FIG. 3.

Crystal Data: C₂₆H₁₀N₄, from CH₂Cl₂, colorless, needle,˜0.300×0.040×0.040 mm, monoclinic, P21/n, a=6.5903(13) Å, b=12.823(3) Å,c=11.659(2) Å, beta=100.32(3)°, Vol.=969.3(3) Å³, Z=2, T=−100° C.,Formula weight=378.38, Density=1.296 mg/m³, μ(MO)=0.08 mm⁻¹.

Example 6 Preparation of 1-Ethylpyrene Thioacetyl Benzene

1-Ethylpyrene thioacetyl benzene can be synthesized according to theprocedure outlined in Example 1 via the reaction scheme shown above.

Example 7 Preparation of 1-Ethylpyrene-4-(2-Fluoro-Cyanobenzene)

1-Ethylpyrene-4-(2-fluoro-cyanobenzene) can be synthesized according tothe procedure outlined in Example 1 via the reaction scheme shown above.

Example 8 Preparation of 1-Ethylpyrene-4-(Pentafluorbenzene)

1-Ethylpyrene-4-(pentafluorbenzene) can be synthesized according to theprocedure outlined in Example 1 via the reaction scheme shown above.

Example 9 Preparation of1-Thioacetyl-4(4′-Fluoro-1′-(Ethynyl)Phenyl)Benzene: PF-PETB

pF-PETB was synthesized according to the procedure outlined in Example 1via the reaction scheme shown above. The compound was recrystallizedfrom ethanol, to give colorless, thin needle crystals whose structure asdetermined from X-ray diffraction analyses is shown in FIG. 4:

Crystal Data: C₁₆H₁₁FOS, from ethanol, colorless, thin needle,0.220×0.040×0.010 mm, monoclinic, C2/c, a=24.998(5) Å, b=9.442(2) Å,c=11.627(3) Å, beta=111.318(4)°, Vol=2556.5(10) Å3, Z=8, T=−100° C.,Formula weight=270.31, Density=1.405 mg/m³, μ(Mo)=0.25 mm⁻¹.

Example 10 Preparation of4-ethynyl(2-fluoro-cyanobenzene)-4′-ethynylphenyl-1(2-fluoro-cyanobenzene):2F2NC3B

This aromatic ethynylene compound was synthesized by palladium (0)/CuIcatalyzed cross coupling reaction of 1,4 diethynyl benzene and4-bromo-2-fluorobenzonitrile according to the scheme shown below:

The resulting compound was subjected to several crystallization stepsuntil pure crystals were obtained. The structure of crystals wasdetermined from X-ray diffraction analysis. The crystal structure asdetermined from X-ray diffraction analyses is shown in FIG. 5.

Crystal Data: C₂₄H₁₀F₂N₂, from hexane/dichloromethane, colorless, plate,˜0.500×0.450×0.030 mm, monoclinic, P21/c, a=14.600(12) Å, b=5.101(4) Å,c=11.553(9) Å, beta=99.926(14)°, Vol=847.5(12) Å3, Z=4, T=−100° C.,Formula weight=182.17, Density=1.428 mg/m³, μ(Mo)=0.10 mm⁻¹.

Example 11 Prophetic

Several heterostructures can be synthesized according to the reactionschemes shown below.

Conjugated heterostructure from2,2′-(p-phenylenebis(6-bromo-4-phenylenequinoline) and 4-ethynylpyridine

Conjugated heterostructure from 1,2-bis(bromophenyl1-cyanovinylene and4-ethynyl pyridine

Conjugated heterostructure from 2,5(4-bromophenyl)1,3,4-oxadiazole and4-ethynyl pyridine

Conjugated heterostructure from1,4-bis[4-bromophenyl)1,3,4-2-yl]benzene-oxadiazole and 4-ethynylpyridine

Example 12 Self-Assembly and Spectroscopic Ellipsometry Measurement

Differences in electrical conducting properties of the conductingmolecules of the invention may be detected by measuring variousspectroscopic and ellipsometric parameters. This example demonstratesvarious differences in those parameters in the compounds made anddisclosed herein, indicating a variation in their electrical conduction.

The compounds used in this example are drawn from the previous examples.These compounds were subjected to self-assembly chemistry on gold, andsilicon substrates. The Au substrates were thin films depositions on Siwafers with a Ti layer for adhesion. The Au substrate was furthercleaned in a UV/ozone plasma cleaner.

The self-assembly was then prepared on the substrates using theprocedures described in C. Zhou, et al, Appl. Phys. Lett. 71, 611, 1997;M. T. Cygan, et al, J. Am. Chem. Soc., 120, 2721-2732, 1998; and J.Chen, et al, Science, Vol 286, pg. 1550, 1999 Optical properties (indexof refraction, “n” and extinction coefficient, “k”) were determined fromvariable angle spectroscopic ellipsometry (VASE) at three incidentangles covering the wavelength range from 143-800 nm, corresponding toan energy range of 1.5-8.67 eV. The samples for ellipsometry consistedof the self-assembled molecules on a gold-coated silicon wafersubstrate. The VASE ellipsometer was manufactured by J. A. WoollamCompany, 645 M Street, Suite 102, Lincoln, Nebr. 68508 USA. Opticalconstants were fit to these data simultaneously, using an optical modelof the film on the substrate. This method is described in O, S. Heavens,Optical Properties of Thin Solid Films, pp. 55-62, Dover, N.Y., 1991.

Two approaches were used in the Ellipsometric modeling: a Cauchy (C) ora Spectral Cauchy (SC). In the Cauchy model fits, the index ofrefraction n of the self-assembled molecules was presumed to have afixed value. Most typically n was set equal to 1.45, and then only thethickness of the self-assembled molecules was fitted. In the SCapproach, the thickness found with the Cauchy model, was then fixed, andthe optical constants, the complex index of refraction n+ik, was thenfitted as a function of wave length. This allowed the determination ofthe spectral variation of the index of refraction and the extinctioncoefficient and gave a direct insight into the optical absorptions andelectronic transitions in the self assembled molecules.

The results are shown in FIGS. 6-11, and below in Table 1. Hexane andlodyne form insulating SAMs and were measured for comparison.

TABLE 1 Electronic X-ray Ellips. Transition Molecule Length LengthEnergies Comp. Ex. 1:  21.5 Å 18.3 Å — Hexadecane Comp. Ex. 2:  13.8 Å5-6 Å — Lodyne Ex. 9: PETB 10.31 Å 14.1 Å 2.7 eV 11.6 Å 15.1 Å Ex. 10:pF-PETB 12.74 Å 12.8 Å 2.95 eV Ex. 11: 3N-PETB 21.87 Å 12.8 Å 4.1 eV Ex.12: 3-PETB 21.87 Å 70.3 Å 4.0 eV Ex 13: 2F2NC3B 21.73 Å 35.0 Å 6.3 eV7.2 eV 7.6 eV Abs. EdgeThese data indicate that (a) the new compounds of the invention areindeed electrical conducting and (b) that the variations made in theplacement and type of the various substituents resulted in changes inthe electrical conductive properties of the compounds.

1. (canceled)
 2. A conducting molecule selected from the groupconsisting of:

3-8. (canceled)